Acrylonitrile

Source: Wikipedia, the free encyclopedia.
Acrylonitrile
Names
Preferred IUPAC name
Prop-2-enenitrile
Other names
Acrylonitrile
2-Propenenitrile
Cyanoethene
Vinyl cyanide (VCN)
Cyanoethylene[1]
Propenenitrile[1]
Vinyl nitrile
Identifiers
3D model (
JSmol
)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
100.003.152 Edit this at Wikidata
EC Number
  • 608-003-00-4
KEGG
RTECS number
  • AT5250000
UNII
UN number 1093
  • InChI=1S/C3H3N/c1-2-3-4/h2H,1H2 checkY
    Key: NLHHRLWOUZZQLW-UHFFFAOYSA-N checkY
  • InChI=1/C3H3N/c1-2-3-4/h2H,1H2
    Key: NLHHRLWOUZZQLW-UHFFFAOYAG
  • N#CC=C
Properties
C3H3N
Molar mass 53.064 g·mol−1
Appearance Colourless liquid
Density 0.81 g/cm3
Melting point −84 °C (−119 °F; 189 K)
Boiling point 77 °C (171 °F; 350 K)
70 g/L
log P 0.19[2]
Vapor pressure 83 mmHg[1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
flammable
reactive
toxic
potential occupational carcinogen[1]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
4
3
2
Flash point −1 °C; 30 °F; 272 K
471 °C (880 °F; 744 K)
Explosive limits
3–17%
Lethal dose or concentration (LD, LC):
500 ppm (rat, 4 h)
313 ppm (mouse, 4 h)
425 ppm (rat, 4 h)[3]
260 ppm (rabbit, 4 h)
575 ppm (guinea pig, 4 h)
636 ppm (rat, 4 h)
452 ppm (human, 1 h)[3]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 2 ppm C 10 ppm [15-minute] [skin][1]
REL (Recommended)
Ca TWA 1 ppm C 10 ppm [15-minute] [skin][1]
IDLH
(Immediate danger)
85 ppm[1]
Safety data sheet (SDS) ICSC 0092
Related compounds
Related nitriles
acetonitrile
propionitrile
Related compounds
acrylic acid
acrolein
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Acrylonitrile is an

toxic at low doses.[5]

Acrylonitrile is one of the components of

Structure and basic properties

Acrylonitrile is an

impurities. It has a pungent odor of garlic or onions.[4]
Its
toxic at low doses.[5]

Production

Acrylonitrile was first synthesized by the French chemist Charles Moureu in 1893.[7] Acrylonitrile is produced by

catalytic ammoxidation of propylene, also known as the SOHIO process. In 2002, world production capacity was estimated at 5 million tonnes per year,[5][8] rising to about 6 million tonnes by 2017.[9] Acetonitrile and hydrogen cyanide are significant byproducts that are recovered for sale.[5] In fact, the 2008–2009 acetonitrile shortage was caused by a decrease in demand for acrylonitrile.[10]

2 CH3−CH=CH2 + 2 NH3 + 3 O2 → 2 CH2=CH−C≡N + 6 H2O

In the SOHIO process,

hydrocyanic acid, and ammonium sulfate (from excess ammonia). A recovery column removes bulk water, and acrylonitrile and acetonitrile are separated by distillation. One of the first useful catalysts was bismuth phosphomolybdate (Bi9PMo12O52) supported on silica.[11] Further improvements have since been made.[5]

Alternative routes

Various

3-hydroxypropionic acid, which are then converted to acrylonitrile by dehydration and ammoxidation.[12][9] The glycerol route begins with its dehydration to acrolein, which undergoes ammoxidation to give acrylonitrile.[13] The glutamic acid route employs oxidative decarboxylation to 3-cyanopropanoic acid, followed by a decarbonylation-elimination to acrylonitrile.[14] Of these, the glycerol route is broadly considered to be the most viable, although none of these green methods are commercially competitive.[12][13]

Uses

Acrylonitrile is used principally as a

styrene-acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylate (ASA), and other synthetic rubbers such as acrylonitrile butadiene (NBR). Hydrodimerization of acrylonitrile[15][16] affords adiponitrile, used in the synthesis of certain nylons
:

2 CH2=CHCN + 2 e + 2 H+ → NCCH2−CH2−CH2−CH2CN

Acrylonitrile is also a precursor in the manufacture of acrylamide and acrylic acid.[5]

Synthesis of chemicals

Hydrogenation of acrylonitrile is one route to propionitrile. Hydrolysis with sulfuric acid gives acrylamide sulfate, CH=CHC(O)NH2·H2SO4. This salt can be converted to acrylamide with treatment with base or to methyl acrylate by treatment with methanol.[5]

The reaction of acrylonitrile with protic nucleophiles is a common route to a variety of specialty chemicals. The process is called cyanoethylation:

YH + H2C=CHCN → Y−CH2−CH2CN

Typical protic nucleophiles are alcohols, thiols, and especially amines.[17]

Acrylonitrile and derivatives, such as 2-chloroacrylonitrile, are

.

Health effects

Acrylonitrile is moderately

It evaporates quickly at room temperature (20 °C) to reach dangerous concentrations;

There are two main excretion processes of acrylonitrile. The primary method is excretion in urine when acrylonitrile is metabolized by being directly conjugated to glutathione. The other method is when acrylonitrile is enzymatically converted into 2-cyanoethylene oxide which will produce cyanide end products that ultimately form thiocyanate, which is excreted via urine.[25] Exposure can thus be detected via blood draws and urine sampling.[18]

Incidents

A large amount of acrylonitrile (approximately 6500 tons) leaked from an industrial polymer plant owned by Aksa Akrilik after the violent 17 August earthquake in Turkey. Over 5000 people were affected and the exposed animals had died.[26] The leak was only noticed by the company 8 hours after the incident. Healthcare workers did not know about the health effects of acrylonitrile and tried to treat the victims with painkillers and IV fluids.[27] One lawyer, Ayşe Akdemir, sued the company with 44 families as the plaintiffs.[27] Aksa Akrilik was sued by 200 residents who were affected by acrylonitrile.[28] An increase in cancer cases in the area was confirmed by the Turkish Medical Association,[28] as the cancer rate in the affected area has increased by 80%, from 1999 to April 2002.[27] In 2003, the owner of Aksa Akrilik has died from lung cancer related to acrylonitrile exposure.[27] As of 2001, this is the largest acrylonitrile leak known.[26]

Occurrence

Acrylonitrile is not naturally formed on Earth. It has been detected at the sub-ppm level at industrial sites. It persists in the air for up to a week. It decomposes by reacting with oxygen and hydroxyl radical to form formyl cyanide and formaldehyde.[29] Acrylonitrile is harmful to aquatic life.[24] Acrylonitrile has been detected in the atmosphere of Titan, a moon of Saturn.[30][31][32] Computer simulations suggest that on Titan conditions exist such that the compound could form structures similar to cell membranes and vesicles on Earth, called azotosomes.[30][31]

References

  1. ^ a b c d e f g h NIOSH Pocket Guide to Chemical Hazards. "#0014". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ "Acrylonitrile_msds".
  3. ^ a b "Acrylonitrile". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. ^ a b "Medical Management Guidelines for Acrylonitrile". Agency for Toxic Substances & Disease Registry. Retrieved 2020-06-10.
  5. ^ .
  6. , retrieved 2023-11-20
  7. ^
  8. ^ "The Sohio Acrylonitrile Process". American Chemical Society National Historic Chemical Landmarks. Archived from the original on 2013-02-23. Retrieved 2013-05-13.
  9. ^ .
  10. .
  11. .
  12. ^ .
  13. ^ .
  14. .
  15. ^ Ellis, Paul G (1972). A radiation-chemical study of the hydrodimerisation of acrylonitrile. UK: Leeds University, Ph D thesis.
  16. .
  17. .
  18. ^ a b "Re-evaluation of Some Organic Chemicals, Hydrazine and Hydrogen Peroxide". IARC Monographs, Volume 71 (1999)
  19. ^ Acrylonitrile Fact Sheet (CAS No. 107-13-1). epa.gov
  20. PMID 21802474
  21. ^ Pu X, Kamendulis LM, Klaunig JE. Acrylonitrile-induced oxidative stress and oxidative DNA damage in male Sprague-Dawley rats. Toxicol Sci. 2009;111(1):64-71. doi:10.1093/toxsci/kfp133
  22. ^ "Acrylonitrile: Carcinogenic Potency Database".
  23. PMID 24248151
    .
  24. ^ a b c "CDC – Acrylonitrile – International Chemical Safety Cards". www.cdc.gov. NIOSH. Retrieved 2015-07-31.
  25. ^ a b Acrylonitrile Fact Sheet: Support Document (CAS No. 107-13-1). epa.gov
  26. ^ a b Nadi Bakırcı (2001). "ENDÜSTRİYEL BİR ÇEVRE FELAKETİ: AKRİLONİTRİL" [AN INDUSTRIAL ENVIRONMENT DISASTER: ACRYLONITRILE]. Turkish Medical Association.
  27. ^ a b c d Fatma Dalokay (30 November 2020). "17 Ağustos 1999 Depremi: Akrilonitril Zehirlenmesi" [17 August 1999 Earthquake: Acrylonitrile Poisoning]. Tabella.
  28. ^ a b "İSO'nun şaşırtan çevre ödülü Aksa'nın". Hürriyet. 26 June 2005.
  29. .
  30. ^ a b Wall, Mike (28 July 2017). "Saturn Moon Titan Has Molecules That Could Help Make Cell Membranes". Space.com. Retrieved 29 July 2017.
  31. ^
    PMID 28782019
    .
  32. ^ Kaplan, Sarah (8 August 2017). "This weird moon of Saturn has some essential ingredients for life". The Washington Post. Retrieved 8 August 2017.

External links